EP0887355B1 - Verfahren zur herstellung von olefinpolymeren - Google Patents

Verfahren zur herstellung von olefinpolymeren Download PDF

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Publication number
EP0887355B1
EP0887355B1 EP97949175A EP97949175A EP0887355B1 EP 0887355 B1 EP0887355 B1 EP 0887355B1 EP 97949175 A EP97949175 A EP 97949175A EP 97949175 A EP97949175 A EP 97949175A EP 0887355 B1 EP0887355 B1 EP 0887355B1
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group
compound
aliphatic hydrocarbon
olefin
catalyst
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EP0887355A4 (de
EP0887355A1 (de
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Hideki Sato
Hiroaki Katayama
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

  • the present invention relates to a method for producing an olefin polymer. More particularly, the present invention relates to a method for producing an olefin polymer using a transition metal compound represented by a metallocene complex, which does not require use of an aromatic hydrocarbon as a solvent.
  • the olefin polymer includes a homopolymer of an olefin and a copolymer of a plurality of olefins.
  • a catalyst for polymerization comprising a transition metal compound, particularly a diimine complex or a transition metal complex containing one or two groups having a cyclopentadiene type anionic skeleton, e.g. a so-called non-metallocene complex or metallocene complex, respectively, and aluminoxane exhibits a high activity.
  • a transition metal compound particularly a diimine complex or a transition metal complex containing one or two groups having a cyclopentadiene type anionic skeleton, e.g. a so-called non-metallocene complex or metallocene complex, respectively, and aluminoxane exhibits a high activity.
  • the metallocene complex is used, an olefin polymer having narrow molecular weight distribution and composition distribution, that is, the resulting olefin polymer exhibits considerably useful feature from industrial point of view. Therefore, a lot of reports have recently been made (e.g. Japanese Patent Publication (K
  • transition metal compounds such as ethylenebis(indenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, and dimethylsilyl (tert-butylamide)(tetramethylcyclopentadienyl)titanium dichloride, are soluble in an aromatic hydrocarbon solvent such as toluene, but hardly dissolve in an aliphatic hydrocarbon solvent. Therefore, the transition metal compound was normally handled in the form of a solution of the aromatic hydrocarbon solvent.
  • the above boron compound is a particulate solid and has a problem that it dissolves in the aromatic hydrocarbon solvent such as toluene to some extent but its solubility in the other solvent, particularly aliphatic hydrocarbon solvent, is very low.
  • the aromatic hydrocarbon solvent such as toluene
  • Such a solvent is liable to remain in a polymer as the product to give off an odor, resulting in a large problem.
  • An object of the present invention is to provide a method of producing an olefin polymer using a transition metal compound, which does not require use of an aromatic hydrocarbon solvent which is liable to remain in a polymer as the product to give off an odor.
  • a method for producing an olefin polymer which comprises homopolymerizing or copolymerizing olefins in the presence of a catalyst for olefin polymerization, comprising the following (A) and (C) as catalyst components, or a catalyst for olefin polymerization, comprising the following (A), (B) and (C) as catalyst components:
  • an aromatic hydrocarbon compound As the solvent for dissolving, suspending or slurrying these catalyst components, an aliphatic hydrocarbon solvent is used.
  • the component(A) of the catalyst for polymerizing an olefin used in the present invention is a dissolved, suspended or slurried transition metal component.
  • the transition metal compound is preferably a compound of Group III-XII or Group of lanthanide of the Periodic Table of the Elements (1993, IUPAC), and various transition metal compounds having an olefin polymerization activity (e.g. metallocene complex, non-metallocene complex can be employed.
  • a transition metal compound of Group IV or lanthanide series is more preferred, and a transition metal compound having at least one cyclopentadiene type anionic skeleton, i.e. metallocene transition metal compound is most preferred.
  • the metallocene transition metal compound is a compound represented by the following general formula (3) : (3) ML a R 3 p-a (wherein M represents a transition metal compound of Group IV or lanthanide series of the Periodic Table of the Elements (1993, IUPAC); L represents a group having a cyclopentadiene type anionic skeleton or a group having a heteroatom, at least one of which is a group having a cyclopentadiene type anionic skeleton, and a plurality of L may be the same or different and may be crosslinked each other; R 3 represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms; a represents a numeral satisfying 0 ⁇ a ⁇ p; and p represents a valence of a transition metal atom M).
  • M represents a transition metal compound of Group IV or lanthanide series of the Periodic Table of the Elements (1993, IUPAC)
  • L represents a group having a cyclopen
  • M is a transition metal compound of Group IV or lanthanide series of the Periodic Table of the Elements (1993, IUPAC).
  • Specific examples of the transition metal atom of Group IV include a titanium atom, a zirconium atom, a hafnium atom, and specific examples of the transition metal atom of lanthanide series include a samarium atom. Among them, titanium atom, zirconium atom or hafnium atom is preferred.
  • L is a group having a cyclopentadiene type anionic skeleton or a group having a heteroatom, at least one of which is a group having a cyclopentadiene type anionic skeleton, and a plurality of L may be the same or different and may be crosslinked each other.
  • Examples of the group having a cyclopentadiene type anionic skeleton include ⁇ 5 -cyclopentadienyl group, ⁇ 5 -substituted cyclopentadienyl group or a polycyclic group having a cyclopentadiene type anionic skeleton.
  • Examples of the substituent of the ⁇ 5 -substituted cyclopentadienyl group include hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms or silyl group having 1 to 20 carbon atoms.
  • Examples of the polycyclic group having a cyclopentadiene type anionic skeleton include ⁇ 5 -indenyl group, and ⁇ 5 -fluorenyl group.
  • Examples of the heteroatom in the group having a heteroatom include nitrogen atom, phosphorous atom, oxygen atom, and sulfur atom.
  • Examples of the group having such a heteroatom include hydrocarbylamino group, hydrocarbylphosphino group, hydrocarbyloxy group, and hydrocarbylthio group, preferably alkoxy group, aryloxy group, alkylthio group, arylthio group, dialkylamino group, diarylamino group, dialkylphosphino group and diarylphosphino group.
  • ⁇ 5 -substituted cyclopentadienyl group examples include ⁇ 5 -methylcyclopentadienyl group, ⁇ 5 -ethylcyclopentadienyl group, ⁇ 5 -n-propylcyclopentadienyl group, ⁇ 5- isopropylcyclopentadienyl group, ⁇ 5 -n-butylcyclopentadienyl group, ⁇ 5 -isobutylcyclopentadienyl group, ⁇ 5 -sec-butylcyclopentadienyl groups, ⁇ 5 -tert-butylcyclopentadienyl group, ⁇ 5 -1,2-dimethylcyclopentadienyl group, ⁇ 5 -1,3-dimethylcyclopentadienyl group, ⁇ 5 -1,2,3-trimethylcyclopentadienyl group, ⁇ 5 -1,2,4-trimethylcyclopentadienyl group,
  • polycyclic group having a cyclopentadiene type anionic skeleton examples include ⁇ 5 -indenyl group, ⁇ 5 -2-methylindenyl group, ⁇ 5 -4-methylindenyl group, ⁇ 5 -4, 5, 6, 7-tetrahydroindenyl group, and ⁇ 5 -fluorenyl group.
  • group having a hetero atom examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, methylthio group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, pyrrolyl group, and dimethylphosphino group.
  • the groups having a cyclopentadiene type anionic skeleton, or the group having a cyclopentadiene type anionic skeleton and the group having a hetero atom may be crosslinked each other.
  • an alkylene group e.g. ethylene group, propylene group
  • a substituted alkylene group e.g. dimethylmethylene group, diphenylmethylene group
  • a substituted silylene group e.g. silylene group, dimethylsilylene group, diphenylsilylene group, tetramethyldisilylene group
  • R 3 in the general formula (3) representing the metallocene transition metal compound is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • a is a numeral satisfying 0 ⁇ a ⁇ p
  • p is a valence of a transition metal atom M.
  • Specific examples of R 3 include a fluorine atom, a chlorine atom, a bromine atom, iodine atom as the halogen atom and methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group as the hydrocarbon group having 1 to 20 carbon atoms.
  • R 3 is preferably a chlorine atom, methyl group or benzyl group.
  • specific examples of the compound wherein the transition metal atom M is a zirconium atom include bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(cyclopentadien
  • zirconium of the above zirconium compounds is replaced by titanium or hafnium.
  • metallocene transition metal compounds may be used alone or in combination of two or more.
  • the component (A) of the catalyst for olefin polymerization used in the present invention is a transition metal compound dissolved, suspended or slurried in the aliphatic hydrocarbon compound, and a transition metal compound dissolved in the aliphatic hydrocarbon compound is preferably used.
  • transition metal compound soluble in such an aliphatic hydrocarbon compound examples include isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, and dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride.
  • the component (B) used in the present invention is a compound dissolved, suspended or slurried in an aliphatic hydrocarbon compound, which is selected from (B1) an organoaluminum compound represented by the general formula E 1 a AlZ 3-a , (B2) a cyclic aluminoxane having a structure represented by the general formula ⁇ -Al(E 2 )-O- ⁇ b hand (B3) a linear aluminoxane having a structure represented by the general formula E 3 ⁇ -Al(E 3 )-O- ⁇ c AlE 3 2 (wherein E 1 to E 3 respectively represents a hydrocarbon group having 1 to 8 carbon atoms, all of E 1 , all of E 2 and all of E 3 may be the same or different; Z represents a hydrogen atom or a halogen atom, and all of Z may be the same or different; a represents a numeral satisfying 0 ⁇ a ⁇ 3; b represents an integer of not less than 2; and c
  • organoaluminum compound (B1) represented by the general formula E 1 a AlZ 3-a include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; and dialkylaluminum hydride such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diiso
  • trialkylaluminum is preferred and triethylaluminum or triisobutylaluminum is more preferred.
  • E 2 and E 3 in (B2) a cyclic aluminoxane having a structure represented by the general formula ⁇ -Al(E 2 )-O- ⁇ b and (B3) a linear aluminoxane having a structure represented by the general formula E 3- ⁇ Al(E 3 )-O- ⁇ c
  • AlE 3 2 include alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, and neopentyl group.
  • b is an integer of not less than 2
  • c is an integer of not less than 1.
  • Each of E 2 and E 3 is preferably methyl group or isobutyl group.
  • b is from 2 to 40 and c is from 1 to 40.
  • the above aluminoxane is prepared by various methods.
  • the method is not specifically limited, and the aluminoxane may be prepared according to a known method.
  • the aluminoxane is prepared by contacting a solution, which is obtained by dissolving a trialkylaluminum (e.g. trimethylaluminum) in a suitable organic solvent (e.g. benzene, aliphatic hydrocarbon) with water.
  • a suitable organic solvent e.g. benzene, aliphatic hydrocarbon
  • a method for preparing the aluminoxane by contacting a trialkylaluminum (e.g. trimethylaluminum) with a metal salt containing crystal water (e.g. copper sulfate hydrate).
  • component (C) in the present invention there can be used one or more boron compounds selected from the following (C1) to (C3):
  • B is a boron atom in the trivalent valence state
  • Q 1 to Q 3 may be the same or different and represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an amino group having 2 to 20 carbon atoms.
  • Q 1 to Q 3 are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • the compound (C1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, and phenylbis(pentafluorophenyl)borane, most preferably tris(pentafluorophenyl)borane.
  • G + represents an inorganic or organic cation
  • B is a boron atom in the trivalent valence state
  • Q 1 to Q 4 are as defined in Q 1 to Q 3 in the above (1).
  • Examples of the G + as an organic cation include triphenylmethyl cation.
  • G + is preferably a carbenium cation.
  • Examples of (BQ 1 Q 2 Q 3 Q 4 ) - include tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate, and tetrakis(3,5-bistrifluoromethylphenyl)borate.
  • ferroceniumtetrakis(pentafluorophenyl)borate 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, and triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate, most preferably triphenylmethyltetrakis(pentafluorophenyl)borate.
  • L represents a neutral Lewis base
  • (L-H) + represents a Br ⁇ nsted acid
  • B represents a boron atom in the trivalent valence state
  • Q 1 to Q 4 are as defined in Q 1 to Q 3 in the above (C1).
  • (L-H) + as a Br ⁇ nsted acid in the compound represented by the general formula (L-H) + (BQ 1 Q 2 Q 3 Q 4 ) - include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium, and triarylphosphonium, and examples of (BQ 1 Q 2 Q 3 Q 4 ) - include those as defined above.
  • component (C), (C2) or (C3) is preferred and triphenylmethyltetrakis(pentafluorophenyl)borate or N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate is particularly preferred. N,N-dimethylaniliniumtetrakis(pehtafluorophenyl)borate is most preferred.
  • a catalyst for olefin polymerization a catalyst for olefin polymerization, obtainable by using the above (A) and (C) as the catalyst component, or a catalyst for olefin polymerization, obtainable by using the above (A), (B) and (C) as the catalyst component is used.
  • a catalyst for olefin polymerization prepared by continuously feeding a part or all of the respective catalyst components in an apparatus for preparing a catalyst, or a catalyst for olefin polymerization prepared by continuously feeding the respective catalyst components in an apparatus for olefin polymerization is used.
  • the respective catalyst components can be used by charging in an arbitrary order, but an arbitrary combination thereof may be used after previous contact.
  • the respective catalyst components are sometimes used in the state suspended or slurried in the aliphatic hydrocarbon compound.
  • the state suspended or slurried in the solvent means the state in which a solid is not completely dissolved in the solvent but solid particles are dispersed in the solvent.
  • the suspended state and slurried state are not particularly distinguished.
  • the sedimentation velocity of each of the catalyst components in the suspended or slurried state is preferably lower than the flow velocity in a pipeline so that each of the catalyst components are not deposited in the pipeline.
  • the solvent used for dissolving, suspending or slurrying in the solvent is not specifically limited as far as it is an aliphatic hydrocarbon compound which causes no problem in use of the respective catalyst components.
  • Specific examples thereof include butane, hexane, heptane, octane, cyclohexane, dodecane, and liquid paraffins.
  • a solvent having a high viscosity so that the sedimentation velocity of the respective catalyst components in the suspended or slurried state is lower than the flow velocity in the pipeline.
  • the viscosity of the solvent is preferably not less than 0.8 mPa ⁇ s (cP (centipoise)), more preferably 1.4 to 1200 mPa ⁇ s (cP), most preferably 1.6 to 50 mPa ⁇ s (cP).
  • solvents having a high viscosity include dodecane, various liquid paraffins, mixed solvents of these with other solvents.
  • liquid paraffins for example, commercially available liquid paraffins having various viscosities within 2 to 2000 mPa ⁇ s (cP) can be used.
  • the viscosity referred to herein means the viscosity at 20°C.
  • Such a high-viscosity solvent is used as the solvent of the above component (C), furthermore, preferably used as the solvent of the above components (C) and (A).
  • a diameter of the pipeline is not specifically limited, but is from 0.5 to 100 mm, preferably from 1 to 50 mm, more preferably from 1.5 to 30 mm.
  • the concentration of the respective catalyst components is appropriately selected according to the conditions such as performances of the apparatus for feeding the respective catalyst components to a polymerization reactor, and the respective catalyst components are preferably used so that the concentration of (A) is normally from 0.01 to 500 ⁇ mol/g, preferably from 0.05 to 100 ⁇ mol/g, more preferably from 0.05 to 50 ⁇ mol/g; the concentration of (B) is normally from 0.01 to 10000 ⁇ mol/g, preferably from 0.1 to 5000 ⁇ mol/g, more preferably from 0.1 to 2000 ⁇ mol/g, in terms of Al atom; and the concentration of (C) is normally from 0.01 to 500 ⁇ mol/g, preferably from 0.05 to 200 ⁇ mol/g, more preferably from 0.05 to 100 ⁇ mol/g.
  • the above component (C) and majorities of the component (A) are soluble in an aromatic hydrocarbon solvent such as toluene to some extent, but hardly dissolve in an aliphatic hydrocarbon solvent.
  • an aromatic hydrocarbon solvent such as toluene
  • the amount of the above component (C) contained in the solution is small, particularly, the component (C) can be fed in a large amount and smaller volume by using a method of feeding the respective catalyst components in the suspended or slurried state in the solvent, favorably.
  • the above component (C) can be fed in the amount of 0.0001 to 800 mmol/liter, preferably 0.001 to 500 mmol/liter, in terms of the number of moles of the boron compound based on the volume of the solvent.
  • the respective catalyst components in the catalyst for olefin polymerization used in the present invention are preferably used so that a molar ratio of the component (B)/the component (A) is within the range from 0.1 to 10000, preferably from 5 to 2000, and a molar ratio of the component (C)/the component (A) is within the range from 0.01 to 100, preferably from 0.5 to 10.
  • olefin which can be applied to the polymerization in the present invention, all of olefins having 2 to 20 carbon atoms can be used and two or more olefins can also be used, simultaneously.
  • the olefin include straight-chain ⁇ -olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1; branched ⁇ -olefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and 5-methyl-2-pentene-1; and vinylcyclohexane.
  • straight-chain ⁇ -olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1
  • Examples of the combination of olefins in the copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, and propylene and butene-1.
  • the present invention can be effectively applied to the preparation of the copolymer of ethylene and ⁇ -olefin (e.g. propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1), particularly.
  • ⁇ -olefin e.g. propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1
  • the polymerization method should not be specifically limited.
  • solvent polymerization or slurry polymerization using an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, as the solvent
  • high-pressure ionic polymerization in the absence of a solvent under high temperature and high pressure gas phase polymerization in a gaseous monomer.
  • the polymerization can be performed in a continuous manner or a batch-wise manner.
  • the preferable polymerization method in the present invention includes a high-temperature solution method of polymerizing an olefin under the conditions of 120 to 250°C and 490 to 4903 kPa (5 to 50 kg/cm 2 ) where the polymer is molten, using a solvent such as cyclohexane and a high-pressure ionic polymerization method of polymerizing an olefin in a super critical fluid state under high temperature and high pressure in the absence of a solvent in the state where the produced polymer is molten.
  • the polymerization is performed under a pressure of at least 29.4 MPa (300 kg/cm 2 ), preferably 34 to 343 MPa (350 to 3500 kg/cm 2 ) at a temperature of at least 130°C, preferably 135 to 350°C.
  • a pressure of at least 29.4 MPa 300 kg/cm 2
  • 34 to 343 MPa 350 to 3500 kg/cm 2
  • a temperature of at least 130°C preferably 135 to 350°C.
  • a stirring type vessel reactor or a tubular reactor can be used as a reactor.
  • the polymerization can be performed in a single reaction zone.
  • the polymerization can also be performed by partitioning one reactor into a plurality of reaction zones or connecting a plurality of reactors in series or parallel.
  • both of a combination of a vessel reactor and another vessel reactor and a combination of a vessel reactor and a tubular reactor are used.
  • polymers having different characteristics can also be produced by changing the temperature, pressure and gas composition of each reaction zone.
  • the respective catalyst components are normally fed to the reactor with a high-pressure pump.
  • the catalyst is preferably in liquid-form, is homogeneously dissolved in a solvent, or is a particle small in a particle diameter and good in dispersity when it is solid insoluble in a solvent.
  • the maximum particle diameter is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, particularly 10 ⁇ m or less, most preferably 5 ⁇ m or less.
  • a maximum particle diameter of the boron compound in (C) is not more than 50 ⁇ m.
  • a catalyst solution is normally handled under an inert gas atmosphere such as nitrogen, or argon so that it is not brought into contact with water and air.
  • the polymerization time is appropriately determined according to the kind of the desired polymer and reactor, and the conditions are not specifically limited.
  • a chain transfer agent such as hydrogen, can also be added to control the molecular weight of the copolymer.
  • Fig. 1 is a flow chart for assisting the understanding of the present invention. This flow chart is a typical example of an embodiment of the present invention, and the present invention is not limited thereto.
  • the resulting organic layer was dried by using anhydrous sodium sulfate and the solvent was removed by using an evaporator. Then, the organic layer was purified by using a silica gel column to obtain 18.4 g (75.7 mmol) of 1-bromo-3-tert-butyl-5-methyl-2-phenol as a colorless oil. The yield was 62%.
  • the polymerization temperature was set to 230°C, a molar ratio of Al atom to Ti atom was set to 60, and a molar ratio of boron atom to Ti atom was set to 4.4.
  • an ethylene-butene-1 copolymer having a melting point of 90.6°C, a molecular weight (Mw) of 64000 and a molecular weight distribution (Mw/Mn) of 1.7 was produced in a rate of 10 tonsper one hour per mol of Ti atom.
  • the resulting suspension was adjusted so that a molar ratio of boron atom to Ti atom becomes 6.0.
  • This mixed suspension and a heptane solution (5.47 ⁇ mol/g) of triisobutylaluminum were prepared in separate vessels, and the respective solutions were continuously fed in the reactor through a pipeline having a diameter of 3.175 mm at a feeding rate of 323 g/hour and 240 g/hour, respectively.
  • the polymerization reaction temperature was set to 205°C and a molar ratio of Al atom to Ti atom was set to 61.7.
  • an ethylene-butene-1 copolymer having a density (without annealing) of 0.873 g/cm 3 , MFR of 6.8 g/10 min., a molecular weight (Mw) of 72000 and a molecular weight distribution (Mw/Mn) of 1.7 was produced in a rate of 98.4 tons per one hour per mol of Ti atom.
  • the resulting suspension was adjusted so that a molar ratio of boron atom to Ti atom becomes 6.0.
  • This mixed suspension and a heptane solution (5.47 ⁇ mol/g) of triisobutylaluminum were prepared in separate vessels, and the respective ones were continuously fed in the reactor through a pipeline having a diameter of 3.175 mm at a feeding rate of 373 g/hour and 283 g/hour, respectively.
  • the polymerization reaction temperature was set to 206°C and a molar ratio of Al atom to Ti atom was set to 63.3.
  • an ethylene-butene-1 copolymer having a density (without annealing) of 0.867 g/cm 3 , a melting point of 42.6°C and a MFR of 11.8 g/10 min. was produced in a rate of 106.3 tons per one hour per mol of Ti atom.
  • the resulting suspension was adjusted so that a molar ratio of boron atom to Ti atom becomes 6.0.
  • This mixed suspension and a heptane solution (5.47 ⁇ mol/g) of triisobutylaluminum were prepared in separate vessels, and the respective ones were continuously fed in the reactor through a pipeline having a diameter of 3.175 mm at a feeding rate of 290 g/hour and 270 g/hour, respectively.
  • the polymerization reaction temperature was set to 205°C and a molar ratio of boron atom to Ti atom was set to 77.2.
  • an ethylene-butene-1 copolymer having a MFR of 13.3 g/10 min. was produced in a rate of 104.5 tons per one hour per mol of Ti atom.
  • a heptane solution obtained by mixing dimethylsilyl (tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride and triisobutylaluminum (the concentrations of the complex and triisobutylaluminum are 0.37 ⁇ mol/g and 18.5 ⁇ mol/g, respectively, and a molar ratio of Al atom to Ti atom is 50) and a suspension (0.71 ⁇ mol/g) of triphenylmethyltetrakis (pentafluorophenyl)borate (a maximum particle diameter of 20 ⁇ m or less) atomized by wet pulverization, suspended in a mixture (a volume ratio of heptane: liquid paraffin 1:4) of heptane and liquid paraffin (Crystol 202, manufactured by Esso Sekiyu K.K.), were prepared in separate vessels, and the respective solutions were continuously fed in the reactor through a pipeline having
  • the polymerization temperature was set to 210°C and a molar ratio of boron atom to Ti atom was set to 3.6.
  • a molar ratio of boron atom to Ti atom was set to 3.6.
  • an ethylene-hexene-1 copolymer having a MFR of 3.8 g/10 min. and a density (without annealing) of 0.889 g/cm 3 was produced in a rate of 28 tons per one hour per mol of Ti atom.
  • an ethylene-hexene-1 copolymer having a MFR of 5.8 g/10 min., a density (without annealing) of 0.888 g/cm 3 , a melting point of 69.8°C and SCB of 32.6 was produced in a rate of 11 tons per one hour per mol of Ti atom.
  • an ethylene-hexene-1 copolymer having a MFR of 55 g/10 min. and a density (without annealing) of 0.886 g/cm 3 was produced in a rate of 13 tons per one hour per mol of Ti atom.

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Claims (9)

  1. Verfahren zur Herstellung eines Olefin-Polymers, gekennzeichnet durch Homopolymerisation eines Olefins oder Copolymerisation von zwei oder mehr Olefinen in Gegenwart eines Katalysators für die Olefin-Polymerisation, umfassend die folgenden
    (A) und (C) als Katalysatorkomponenten, oder eines Katalysators für die Olefin-Polymerisation, umfassend die folgenden (A), (B) und (C) als Katalysatorkomponenten:
    (A) eine Übergangsmetallverbindung, gelöst, suspendiert oder aufgeschlämmt in einer aliphatischen Kohlenwasserstoffverbindung;
    (B) eine Verbindung, gelöst, suspendiert oder aufgeschlämmt in einer aliphatischen Kohlenwasserstoffverbindung, ausgewählt aus den folgenden (B1) bis (B3):
    (B1) einer Organoaluminiumverbindung der allgemeinen Formel E1 aAlZ3-a;
    (B2) einem cyclischen Aluminoxan mit einer Struktur der allgemeinen Formel {-Al(E2)-O-}b; und
    (B3) einem linearen Aluminoxan mit einer Struktur der allgemeinen Formel E3{-Al(E3)-O-}cAlE3 2,
    wobei E1 bis E3 jeweils einen Kohlenwasserstoffrest mit 1 bis 8 Kohlenstoffatomen darstellen und alle E1, E2 und E3 gleich oder verschieden sein können; Z ein Wasserstoffatom oder ein Halogenatom darstellt, und alle Z gleich oder verschieden sein können; a eine Zahl darstellt, die 0 < a ≤ 3 erfüllt; b eine ganze Zahl von nicht weniger als 2 darstellt; und c eine ganze Zahl von nicht weniger als 1 darstellt, und
    (C) mindestens eine Borverbindung, suspendiert oder aufgeschlämmt in einer aliphatischen Kohlenwasserstoffverbindung, ausgewählt aus den folgenden (C1) bis (C3):
    (C1) einer Borverbindung der allgemeinen Formel BQ1Q2Q3;
    (C2) einer Borverbindung der allgemeinen Formel G+(BQ1Q2Q3Q4)-; und
    (C3) einer Borverbindung der allgemeinen Formel (L-H)+(BQ1Q2Q3Q4)-,
    wobei B ein Boratom im dreiwertigen Valenzzustand bedeutet; Q1 bis Q4 gleich oder verschieden sein können und ein Halogenatom, einen Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, einen halogenierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, einen substituierten Silylrest mit 1 bis 20 Kohlenstoffatomen, einen Alkoxyrest mit 1 bis 20 Kohlenstoffatomen oder einen Aminorest mit 2 bis 20 Kohlenstoffatomen bedeuten; G+ ein anorganisches oder organisches Kation bedeutet; L eine neutrale Lewis-Base darstellt; und (L-H)+ eine Brönsted-Säure bedeutet,
    wobei der Katalysator für die Olefin-Polymerisation ein Katalysator für die Olefin-Polymerisation ist, der durch kontinuierliches Zuführen eines Teils oder der gesamten jeweiligen Katalysatorkomponenten zu einer Vorrichtung zur Herstellung eines Katalysators hergestellt wird, oder ein Katalysator für die Olefin-Polymerisation ist, der durch kontinuierliches Zuführen der jeweiligen Katalysatorkomponenten zu einer Vorrichtung zur Olefin-Polymerisation hergestellt wird, und
    wobei die aliphatische Kohlenwasserstoffverbindung in (C) eine aliphatische Kohlenwasserstoffverbindung mit einer Viskosität von nicht weniger als 0,8 mPa·s (cP) bei 20°C ist.
  2. Verfahren zur Herstellung eines Olefin-Polymers nach Anspruch 1, wobei (A) eine Übergangsmetallverbindung, gelöst in einer aliphatischen Kohlenwasserstoffverbindung, ist.
  3. Verfahren zur Herstellung eines Olefin-Polymers nach Anspruch 1, wobei die Übergangsmetallverbindung eine Übergangsmetallverbindung ist, die einen Rest mit mindestens einem anionischen Gerüst vom Cyclopentadien-Typ enthält.
  4. Verfahren zur Herstellung eines Olefin-Polymers nach Anspruch 1, wobei (B) Triethylaluminium, Triisobutylaluminium, Methylaluminoxan oder Isobutylaluminoxan, gelöst, suspendiert oder aufgeschlämmt in einer aliphatischen Kohlenwasserstoffverbindung, ist.
  5. Verfahren zur Herstellung eines Olefin-Polymers nach Anspruch 1, wobei (C) N,N-Dimethylaniliniumtetrakis(pentafluorphenyl)borat oder Triphenylmethyltetrakis-(pentafluorphenyl)borat, suspendiert oder aufgeschlämmt in einer aliphatischen Kohlenwasserstoffverbindung, ist.
  6. Verfahren zur Herstellung eines Olefin-Polymers nach einem der Ansprüche 1 bis 5, wobei die aliphatischen Kohlenwasserstoffverbindungen in (C) und (A) aliphatische Kohlenwasserstoffverbindungen mit einer Viskosität von 1,6 bis 50 mPa·s (cP) bei 20°C sind.
  7. Verfahren zur Herstellung eines Olefin-Polymers nach einem der Ansprüche 1 bis 5, wobei ein maximaler Teilchendurchmesser der Borverbindung in (C) nicht mehr als 50 µm beträgt.
  8. Verfahren zur Herstellung eines Olefin-Polymers nach einem der Ansprüche 1 bis 7, wobei (C) der Vorrichtung zur Polymerisation über eine Rohrleitung mit einem Durchmesser von 0,5 bis 100 mm zugeführt wird.
  9. Verfahren zur Herstellung eines Olefin-Polymers nach einem der Ansprüche 1 bis 5, wobei das Olefin-Polymer ein Copolymer ist, das Ethylen und α-Olefin umfasst.
EP97949175A 1996-12-20 1997-12-19 Verfahren zur herstellung von olefinpolymeren Expired - Lifetime EP0887355B1 (de)

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WO2020174346A1 (ko) 2019-02-28 2020-09-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
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WO1998028341A1 (en) 1998-07-02
KR19990087052A (ko) 1999-12-15
WO1998028342A1 (en) 1998-07-02
EP0889062A1 (de) 1999-01-07
EP1582525B1 (de) 2014-12-17
EP0889062B1 (de) 2005-08-03
EP0887355A4 (de) 2001-10-24
EP2324918A2 (de) 2011-05-25
CN1216553A (zh) 1999-05-12
WO1998028343A1 (en) 1998-07-02
DE69733883D1 (de) 2005-09-08
DE69736631T2 (de) 2007-09-13
DE69733883T2 (de) 2006-06-01
EP1582525A2 (de) 2005-10-05
DE19781602T1 (de) 1999-03-11
EP0889062A4 (de) 2002-05-15
EP2324918A3 (de) 2013-12-04
EP0887355A1 (de) 1998-12-30
US6184319B1 (en) 2001-02-06
DE69736631D1 (de) 2006-10-19
EP1582525A3 (de) 2006-06-07
US6613850B1 (en) 2003-09-02

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